The present invention relates to laundry detergent compositions which provide enhanced hydrophilic soil, inter alia, clay, removal benefits. The laundry detergent compositions of the present invention combine zwitterionic polyamines and a surfactant system which comprises mid-chain branched surfactants inter alia mid-chain branched alkyl sulphonates. The present invention further relates to methods for cleaning fabric having heavy clay soil deposits.
Fabric, especially clothing, can become soiled with a variety of foreign substances ranging from hydrophobic stains (grease, oil) to hydrophilic stains (clay). The level of cleaning which is necessary to remove said foreign substances depends to a large degree upon the amount of stain present and the degree to which the foreign substance has contacted the fabric fibers. Grass stains usually involve direct abrasive contact with vegetative matter thereby producing highly penetrating stains. Clay soil stains, although in some instances contacting the fabric fibers with less force, nevertheless provide a different type of soil removal problem du to the high degree of charge associated with the clay itself. This high surface charge density may act to repel some laundryadjunct ingredients, inter alia, clay dispersants, thereby resisting any appreciable solublizing of the clay into the laundry liquor.
A surfactant per se is not all that is necessary to remove unwanted clay soils and stains. In fact, not all surfactants work equally well on all types of stains. In addition to surfactants, polyamine hydrophilic soil dispersants are added to laundry detergent compositions to xe2x80x9ccarry awayxe2x80x9d clay soils from the fabric surface and to remove the possibility that the clay soil will be re-deposited upon the fabric. However, unless the clay can be initially solublized away from the fabric fiber, especially in the case of hydrophilic fibers, inter alia, cotton, there will be nothing in solution for the dispersants to chelate.
There is a long felt need in the art for laundry detergent compositions which can effectively solublize embedded clay and other hydrophilic soils from fabric. There has further been a long felt need for a method for cleaning hydrophilic soils from fabric wherein the hydrophilic soils are effectively solublized into the laundry liquor.
The present invention meets the aforementioned needs in that it has been surprisingly discovered that certain zwitterionic polyamines in combination with a surfactant system comprising one or more mid-chain branched surfactants provides enhance removal of clay and other hydrophilic soils from fabric.
The first aspect of the present invention relates to a laundry detergent composition comprising:
a) from about 0.01%, preferably from about 0.1%, more preferably from 1%, most preferably from 3% to about 20%, preferably to about 10%, more preferably to about 5% by weight, of a zwitterionic polymer which comprises a polyamine backbone wherein one or more of said polyamine backbone amino units are quaternized and wherein said polyamine backbone is substituted by one or more units capable of having an anionic charge such that the number of anionic units present in said zwitterionic polymer exceeds the number of backbone quaternized units;
b) from about 0.01%, preferably from about 0.1%, more preferably from about 1% to about 100%, preferably to about 80% by weight, preferably to about 60%, most preferably to about 30% by weight, of a surfactant system comprising one or more mid-chain branched surfactants selected from the group consisting of mid-chain branched alkyl sulfates, mid-chain branched alkoxy sulfates, mid-chain branched aryl sulphonates, and mixtures thereof; and
c) the balance carriers and adjunct ingredients.
The present invention further relates to granular laundry detergent compositions which comprise a surfactant system wherein said surfactant system comprises from about 0.01%, preferably from about 0.1% more preferably from about 1% to about 100%, preferably to about 80% by weight, preferably to about 60%, most preferably to about 30% by weight, of a surfactant which is not a mid-chain branched surfactant, said surfactant selected from the group consisting of anionic, cationic, zwitterionic, nonionic, ampholytic surfactants, and mixtures thereof.
The present invention also relates to laundry detergent compositions which comprise zwitterionic polyamines having a hydrophilic backbone and an anionic tether which when taken together comprises a net anionic charge of at least 1, preferably at least 2, more preferably at least 3.
Another aspect of the present invention relates to a granular laundry detergent composition comprising:
a) from about 0.01%, preferably from about 0.1%, more preferably from 1%, most preferably from 3% to about 20%, preferably to about 10%, more preferably to about 5% by weight, of a zwitterionic polymer which comprises a polyamine backbone, said backbone comprising two or more amino units wherein at least one of said amino units is quaternized and wherein at least one amino unit is substituted by one or more moieties capable of having an anionic charge wherein further the number of amino unit substitutions which comprise an anionic moiety is less than or equal to the number of quaternized backbone amino units;
b) from about 0.01%, preferably from about 0.1% more preferably from about 1% to about 100%, preferably to about 80% by weight, preferably to about 60%, most preferably to about 30% by weight, of a surfactant system comprising one or more mid-chain branched surfactants selected from the group consisting of mid-chain branched alkyl sulfates, mid-chain branched alkoxy sulfates, mid-chain branched aryl sulphonates, and mixtures thereof; and
c) the balance carriers and adjunct ingredients.
A further aspect of the present invention relates to nil bleach compositions which comprise:
a) from about 0.01%, preferably from about 0.1%, more preferably from 1%, most preferably from 3% to about 20%, preferably to about 10%, more preferably to about 5% by weight, of a zwitterionic polyamine according to the present invention;
b) from about 0.01%, preferably from about 0.1% more preferably from about 1% to about 100%, preferably to about 80% by weight, preferably to about 60%, most preferably to about 30% by weight, of a surfactant system comprising:
i) from 0% to 80% by weight, of a mid-chain branched alkyl sulfate surfactant, a mid-chain branched alkyl alkoxy sulfate surfactant, and mixtures thereof;
ii) from 0% to 80% by weight, of a mid-chain branched aryl sulfonate surfactant;
iii) optionally from 0.01% by weight, of a surfactant selected from the group consisting of anionic, nonionic, cationic, zwitterionic, ampholytic surfactants, and mixtures thereof;
c) from about 0.001% by weight, of a detersive enzyme, said enzyme selected from the group consisting of protease, amylases, lipases, cellulases, peroxidases, hydrolases, cutinases, mannanases, xyloglucanases, and mixtures thereof; and
d) the balance carriers and adjunct ingredients.
A yet further aspect of the present invention relates to nil bleach compositions which comprise:
a) from about 0.01%, preferably from about 0.1%, more preferably from 1%, most preferably from 3% to about 20%, preferably to about 10%, more preferably to about 5% by weight, of a zwitterionic polyamine according to the present invention;
b) from about 0.01%, preferably from about 0.1% more preferably from about 1% to about 100%, preferably to about 80% by weight, preferably to about 60%, most preferably to about 30% by weight, of a surfactant system comprising:
i) from 0% to 80% by weight, of a mid-chain branched alkyl sulfate surfactant, a mid-chain branched alkyl alkoxy sulfate surfactant, and mixtures thereof;
ii) from 0% to 80% by weight, of a mid-chain branched aryl sulfonate surfactant;
iii) optionally from 0.01% by weight, of a surfactant selected from the group consisting of anionic, nonionic, cationic, zwitterionic, ampholytic surfactants, and mixtures thereof;
c) from about 1 ppb (0.0000001%), preferably from about 100 ppb (0.00001%), more preferably from about 500 ppb (0.00005%), most preferably from about 1 ppm (0.0001%) to about 99.9%, preferably to about 50%, more preferably to about 5%, most preferably to about 500 ppm (0.05%) by weight, of a transition-metal fabric cleaning catalyst; and
d) the balance carriers and adjunct ingredients.
A yet further aspect of the present invention relates to a handwash laundry detergent composition comprising:
a) from about 0.01%, preferably from about 0.1%, more preferably from 1%, most preferably from 3% to about 20%, preferably to about 10%, more preferably to about 5% by weight, of a zwitterionic polymer which comprises a polyamine backbone wherein one or more of said polyamine backbone amino units are quaternized and wherein said polyamine backbone is substituted by one or more units capable of having an anionic charge such that the value of the charge ratio, Qr, is from greater than about 1 to about 4, preferably to about 2, where said Qr, is defined as:       Q    r    =            ∑              q        anionic                    ∑              q        cationic            
wherein qanionic is an anionic unit and qcationic represents a quaternized backbone nitrogen;
b) from about 0.01%, preferably from about 0.1% more preferably from about 1% to about 100%, preferably to about 80% by weight, preferably to about 60%, most preferably to about 30% by weight, of a surfactant system comprising one or more mid-chain branched surfactants selected from the group consisting of mid-chain branched alkyl sulfates, mid-chain branched alkoxy sulfates, mid-chain branched aryl sulphonates, and mixtures;
c) from about 1%, preferably from about 5%, more preferably from about 10%, most preferably from about 15% to about 80%, preferably to about 50%, more preferably to about 30% by weight, of a detergent builder; and
d) the balance carriers and adjunct ingredients.
Included in the objects of the present invention are laundry detergent compositions which comprise a high level of a builder, said compositions suitable for use in area wherein laundering is conducted by hand in high hardness water.
The present invention also relates to a method for removing hydrophilic stains from fabric by contacting fabric in need of cleaning with an aqueous solution comprising at least 1 ppm (0.0001%), preferably at least 5 ppm (0.0005%), more preferably at least 10 ppm (0.001%) of the zwitterionic polymer.
These and other objects, features and advantages will become apparent to those of ordinary skill in the art from a reading of the following detailed description and the appended claims. All percentages, ratios and proportions herein are by weight, unless otherwise specified. All temperatures are in degrees Celsius (xc2x0 C.) unless otherwise specified. All documents cited are in relevant part, incorporated herein by reference.
The present invention relates to the surprising discovery that the combination of a zwitterionic polyamine having a hydrophilic backbone and a surfactant system which comprises at least one mid-chain branched surfactant provides enhanced benefits for removal of clay soil from fabric especially clothing. It has been surprisingly discovered that the formulator, by selecting the relative degree of quaternization of the polyamine backbone and the type of anionic units which substitute the polyamine backbone, is able to form a zwitterionic polymer which can be tailored for optimization depending upon the desired execution. Preferably, as described herein below, the zwitterionic polymers which are incorporated into granular laundry detergent compositions typically have an excess number of anionic units relative to the number of quaternized backbone nitrogens.
In fact, it has been surprisingly discovered that the zwitterionic polymers of the present invention overcome the problems which occur due to high soil loading, inter alia, loss of surfactant strength when used in combination with one or more mid-chain branched surfactants. The issue of high soil loading is especially germane to the consumer who hand washes fabric thereby exposing the fabric which is laundered at the end of the laundry queue to laundry liquors which are already highly saturated with soils.
It has also been surprisingly discovered that the zwitterionic polymers of the present invention have, in some embodiments, enhanced soil removal properties in high water hardness uses.
For the purpose of the present invention the term xe2x80x9chardnessxe2x80x9d relates to the amount of cations, calcium, inter alia, which are dissolved in the water and which tend to diminish the surfactancy and cleaning capacity of surfactants. The term xe2x80x9chard waterxe2x80x9d is a relative term and for the purposes of the present invention, water having at least xe2x80x9c12 grams per gallon water (gpg, xe2x80x9cAmerican grain hardnessxe2x80x9d units) of calcium ionxe2x80x9d is defined as xe2x80x9chigh hardnessxe2x80x9d and water having at least xe2x80x9c18 gpg of calcium ionxe2x80x9d is defined as xe2x80x9cvery high hardnessxe2x80x9d.
For the purposes of the present invention the term xe2x80x9ccharge ratioxe2x80x9d, Qr, is defined herein as xe2x80x9cthe quotient derived from dividing the sum of the number of anionic units present excluding counter ions by the sum of the number of quaternary ammonium backbone unitsxe2x80x9d. The charge ratio is defined by the expression:       Q    r    =            ∑              q        anionic                    ∑              q        cationic            
wherein qanionic is an anionic unit, inter alia, xe2x80x94SO3M, as defined herein below and qcationic represents a quaternized backbone nitrogen.
For the purposes of the present invention the term xe2x80x9canionic characterxe2x80x9d, xcex94Q, is defined herein as xe2x80x9cthe sum of the number of anionic units which comprise the zwitterionic polymer minus the number of quaternary ammonium backbone unitsxe2x80x9d. The greater the excess number of anionic units, the greater the anionic character of the zwitterionic polymer. It will be recognized by the formulator that some anionic units may have more than one unit which has a negative charge. For the purposes of the present invention units having more than one negatively charged moiety, xe2x80x94CH2CH(SO3M)CH2SO3M, inter alia, will have each moiety capable of having a negative charge counted toward the sum of anionic units, therefore, this unit will count as 2 anionic units. The anionic character is defined by the expression:
xcex94Q=xcexa3qanionicxe2x88x92xcexa3qcationic
wherein qanionic and qcationic are the same as defined herein above.
Those of skill in the art will realize that the greater the number of amine units which comprise the polyamine backbones of the present invention the greater the number of potential cationic units will be contained therein. For the purposes of the present invention the term xe2x80x9cdegree of quaternizationxe2x80x9d is defined herein as xe2x80x9cthe number of backbone units which are quaternized divided by the number of backbone units which comprise the polyamine backbonexe2x80x9d. The degree of quaternization, Q(+), is defined by the expression:       Q    ⁡          (      +      )        =            ∑              quaternized        ⁢                  xe2x80x83                ⁢        backbone        ⁢                  xe2x80x83                ⁢        nitrogens                    ∑              quaternized        ⁢                  xe2x80x83                ⁢        backbone        ⁢                  xe2x80x83                ⁢        nitrogens            
wherein a polyamine having all of the quaternizable backbone nitrogens quaternized will have a Q(+) equal to 1. For the purposes of the present invention the term xe2x80x9cquaternizable nitrogenxe2x80x9d refers to nitrogen atoms in the polyamine backbone which are capable of forming quaternary ammonium ions. This excludes nitrogens not capable of ammonium ion formation, inter alia, amides.
As described herein below, a key aspect of the present invention is the finding that the formulator, by adjusting the parameters Qr, xcex94Q, and Q(+), will be capable of customizing a polymer for formulation into any type of laundry detergent composition having enhanced particulate soil removal benefits throughout a wide variety of settings, for example as a function of (1) the nature of the polymeric structure itself (e.g., EO level, MW, length and HLB of the amine backbone, etc.), (2) the detergent matrix (e.g., pH, type of surfactant, free hardness level), (3) the particular embodiment (e.g., granular, liquids, gel, structured liquid, tablet, non-aqueous, etc.), and (4) desired benefit (e.g., clay stain removal, whiteness, dingy cleaning, etc.). Therefore, in one desired embodiment the zwitterionic polymers of the present invention may have a Qr of from about 1 to about 2, whereas another embodiment will employ zwitterionic polymers having a Qr greater than 2. Specific embodiments, as described herein below, may require a Qr significantly less than 1 or even zero.
Granular laundry detergent compositions per se may comprise clay soil dispersants which chelate the cationic clay particles in solution and hold the particles in solution until they are removed during the rinsing process thus preventing the particles from re-depositing upon the fabric surface. Two examples of preferred hydrophilic dispersants which are further described herein below are as follows: (1) a dispersant which comprises a polyethyleneimine backbone having an average molecular weight of about 189 daltons and in which each nitrogen which comprises said backbone has the appended hydrogen atom(s) replaced by an ethyleneoxy unit having from 15 to 18 residues on average. This preferred ethoxylated polyethyleneimine dispersant is herein after referred to as PEI 189 E15-18. This dispersant is highly effective in dispersing clay soils once the clay soils are removed from fabric. (2) a dispersant which comprises a hexamethylene diamine backbone and in which each nitrogen comprising said backbone has the appended hydrogen atom replaced by an ethyleneoxy unit from about 15 to 25 residues on average. This preferred ethoxylated polyethyleneimine dispersant is herein after referred to as HMD E15-25. This dispersant is also highly effective in dispersing clay soils once the clay soils are removed from fabric.
Subtle changes to the structure of polyalkyleneimines can provide profound changes to the properties thereof. For example, a preferred hydrophobic dispersant capable of dispersing soot, grime, oils, carbonaceous material, comprises a polyethyleneimine having a backbone with an average molecular weight of about 1800 daltons and in which each nitrogen which comprises said backbone has the appended hydrogen atom replaced by an ethyleneoxy unit having from about 0.5 to about 10 residues on average, preferably an average of 7 residues, for example, PEI 1800 E7. The ability to affect profound changes in the properties of polyamines by making small changes to the structure of said polyamines is known and appreciated throughout the laundry art.
Knowing the propensity of these polyamines to exhibit activity in the aqueous laundry liquor, it is therefore surprising and highly unexpected that zwitterionic polyamines having hydrophilic backbone components would act synergistically with certain mid-chain branched surfactants to enhance the removal of clay and other hydrophilic soils directly from fabric fiber itself. Without wishing to be bound by theory it is believed the zwitterionic polyamines of the present invention interact with the mid-chain branched surfactants in a manner which makes clay and other cationic surfaces more anionic in nature. It is believed this system absorbs the modified clay particles from the fiber surface and the inherent agitation associated with the laundry process (for example, the agitation provided by an automatic washing machine) acts to break the once formed complexes loose from the fabric surface and disperse them into solution. The clay and other hydrophilic particles which are removed by the compositions of the present invention are those types of stains or particles which are not removed by normal surfactant/dispersant systems.
Although other surfactants, inter alia, non mid-chain branched sulphonates and sulphates, nonionic surfactants, are highly desirable components of the herein described granular laundry detergent compositions, their absence or presence does not affect the ability of the zwitterionic polyamine/mid-chain branched surfactant system to enhance clay soil removal.
The present invention also relates to the surprising discovery that the combination of a zwitterionic polyamine having a hydrophilic backbone and a surfactant system which comprises at least one mid-chain branched surfactant provides enhanced benefits for removal of clay soil from fabric without the need for a peroxygen bleaching, inter alia, NOBS/perborate, in a liquid laundry detergent matrix when said polyamine and surfactant are combined with one or more transition-metal fabric cleaning catalysts. In addition, the present invention relates to a zwitterionic polymer/surfactant system which is compatible of providing enhanced cleaning together with one or more enzymes. Preferably, as described herein below, the zwitterionic polymers which are incorporated into liquid laundry detergent compositions have an excess number of quaternized backbone nitrogens relative to the number of anionic units which are present.
The laundry detergent compositions of the present invention may take any form, for example, solid, including granular, powder, tablet, or liquid, including gels, paste, thixotropic liquids, etc.
The following is a detailed description of the require elements of the present invention.
The zwitterionic polyamines of the present invention comprise from about 0.01%, preferably from about 0.1%, more preferably from 1%, most preferably from 3% to about 20%, preferably to about 10%, more preferably to about 5% by weight, of the final laundry detergent composition. The present invention relates to granular laundry detergent compositions which can take any solid, particle, or other granular form. In another embodiment the zwitterionic polymers of the present invention are suitable for use in liquid laundry detergent compositions, inter alia, gels, thixotropic liquids, and pourable liquids (i.e., dispersions, isotropic solutions). The zwitterionic polymers of the present invention are comprised of a polyamine backbone wherein the backbone units which connect the amino units can be modified by the formulator to achieve varying levels of product enhancement, inter alia, boosting of clay soil removal by surfactants, greater effectiveness in high soil loading usage. In addition to modification of the backbone compositions, the formulator may preferably substitute one or more of the backbone amino unit hydrogens by other units, inter alia, alkyleneoxy units having a terminal anionic moiety. In addition, the nitrogens of the backbone may be oxidized to the N-oxide. Preferably at least two of the nitrogens of the polyamine backbones are quaternized.
For the purposes of the present invention xe2x80x9ccationic unitsxe2x80x9d are defined as xe2x80x9cunits which are capable of having a positive chargexe2x80x9d. For the purposes of the zwitterionic polyamines of the present invention the cationic units are the quaternary ammonium nitrogens of the polyamine backbones. For the purposes of the present invention xe2x80x9canionic unitsxe2x80x9d are defined as xe2x80x9cunits which are capable of having a negative chargexe2x80x9d. For the purposes of the zwitterionic polyamines of the present invention the anionic units are xe2x80x9cunits which alone, or as a part of another unit, substitute for hydrogens along the polyamine backbonexe2x80x9d a non-limiting example of which is a xe2x80x94(CH2CH2O)20SO3Na which is capable of replacing a backbone hydrogen.
The zwitterionic polyamines of the present invention have the formula:
[Jxe2x80x94R]nxe2x80x94J
wherein the [Jxe2x80x94R] units represent the amino units which comprise the main backbone and any branching chains. Preferably the zwitterionic polyamines prior to modification, inter alia, quaternization, substitution of an amino unit hydrogen with an alkyleneoxy unit, have backbones which comprise from 2 to about 100 amino units. The index n which describes the number of backbone units present is further described herein below.
J units are the backbone amino units, said units are selected from the group consisting of:
i) primary amino units having the formula:
(R1)2N;
ii) secondary amino units having the formula:
xe2x80x83xe2x80x94R1N;
iii) tertiary amino units having the formula: 
iv) primary quaternary amino units having the formula: 
v) secondary quaternary amino units having the formula: 
vi) tertiary quaternary amino units having the formula: 
vii) primary N-oxide amino units having the formula: 
viii) secondary N-oxide amino units having the formula: 
ix) tertiary N-oxide amino units having the formula: 
x) and mixtures thereof.
B units which have the formula:
[Jxe2x80x94R]xe2x80x94
represent a continuation of the zwitterionic polyamine backbone by branching. The number of B units present, as well as, any further amino units which comprise the branches are reflected in the total value of the index n.
The backbone amino units of the zwitterionic polymers are connected by one or more R units, said R units are selected from the group consisting of:
i) C2-C12 linear alkylene, C3-C12 branched alkylene, or mixtures thereof; preferably C3-C6 alkylene. When two adjacent nitrogens of the polyamine backbone are N-oxides, preferably the alkylene backbone unit which separates said units are C4 units or greater.
ii) alkyleneoxyalkylene units having the formula:
xe2x80x94(R2O)w(R3xe2x80x94
wherein R2 is selected from the group consisting of ethylene, 1,2-propylene, 1,3-propylene, 1,2-butylene, 1,4-butylene, and mixtures thereof; R3 is C2-C8 linear alkylene, C3-C8 branched alkylene, phenylene, substituted phenylene, and mixtures thereof; the index w is from 0 to about 25. R2 and R3 units may also comprise other backbone units. When comprising alkyleneoxyalkylene units, in one embodiment R2 and R3 units are each preferably ethylene or mixtures of ethylene, propylene and butylene, more preferably ethylene; in another embodiment R2 and R3 units are preferably mixtures of ethylene, propylene and butylene; the index w is from 1, preferably from about 2 to about 10, preferably to about 6.
iii) hydroxyalkylene units having the formula: 
wherein R4 is hydrogen, C1-C6 alkyl, xe2x80x94(CH2)u(R2O)t(CH2)uY, and mixtures thereof. When R units comprise hydroxyalkylene units, R4 is preferably hydrogen or xe2x80x94CH2)u(R2O)t(CH2)uY wherein the index t is greater than 0, preferably from 10 to 30; the index u is from 0 to 6; and Y is preferably hydrogen or an anionic unit, more preferably xe2x80x94SO3M. The indices x, y, and z are each independently from 1 to 6, preferably the indices are each equal to 1 and R4 is hydrogen (2-hydroxypropylene unit) or (R2O)tY, or for polyhydroxy units y is preferably 2 or 3. A preferred hydroxyalkylene unit is the 2-hydroxypropylene unit which can, for example, be suitably formed from glycidyl ether forming reagents, inter alia, epihalohydrin.
iv) hydroxyalkylene/oxyalkylene units having the formula: 
wherein R2, R4, and the indices w, x, y, and z are the same as defined herein above. X is oxygen or the amino unit xe2x80x94NR4xe2x80x94, the index r is 0 or 1. The indices j and k are each independently from 1 to 20. When alkyleneoxy units are absent the index w is 0. Non-limiting examples of preferred hydroxyalkylene/oxyalkylene units have the formula: 
v) carboxyalkyleneoxy units having the formula: 
wherein R2, R3, X, r, and w are the same as defined herein above. Non-limiting examples of preferred carboxyalkyleneoxy units include: 
vi) backbone branching units having the formula: 
wherein R4 is hydrogen, C1-C6 alkyl, xe2x80x94CH2)u(R2O)t(CH2)uY, and mixtures thereof. When R units comprise backbone branching units, R4 is preferably hydrogen or xe2x80x94CH2)u(R20)txe2x80x94(CH2)uY wherein the index t is greater than 0, preferably from 10 to 30; the index u is from 0 to 6; and Y is hydrogen, C1-C4 linear alkyl, xe2x80x94N(R1)2, an anionic unit, and mixtures thereof; preferably Y is hydrogen, or xe2x80x94N(R1)2. A preferred embodiment of backbone branching units comprises R4 equal to xe2x80x94(R2O)tH. The indices x, y, and z are each independently from 0 to 6.
vii) The formulator may suitably combine any of the above described R units to make a zwitterionic polyamine having a greater or lesser degree of hydrophilic character.
R1 units are the units which are attached to the backbone nitrogens. R1 units are selected from the group consisting of:
i) hydrogen; which is the unit typically present prior to any backbone modification.
ii) C1-C22 alkyl, preferably C1-C4 alkyl, more preferably methyl or ethyl, most preferably methyl. A preferred embodiment of the present invention in the instance wherein R1 units are attached to quaternary units (iv) or (v), R1 is the same unit as quaternizing unit Q. For example a J unit having the formula: 
iii) C7-C22 arylalkyl, preferably benzyl.
iv) xe2x80x94[CH2CH(OR4)CH2O]s(R2O)tY; wherein R2 and R4 are the same as defined herein above, preferably when R1 units comprise R2 units, R2 is preferably ethylene. The value of the index s is from 0 to 5. For the purposes of the present invention the index t is expressed as an average value, said average value from about 0.5 to about 100. The formulator may lightly alkyleneoxylate the backbone nitrogens in a manner wherein not every nitrogen atom comprises an R1 unit which is an alkyleneoxy unit thereby rendering the value of the index t less than 1.
v) Anionic units as described herein below.
vi) The formulator may suitably combine one or more of the above described R1 units when substituting the backbone of the zwitterionic polymers of the present invention.
Q is a quaternizing unit selected from the group consisting of C1-C4 linear alkyl, benzyl, and mixtures thereof, preferably methyl. As described herein above, preferably Q is the same as R1 when R1 comprises an alkyl unit. For each backbone N+ unit (quaternary nitrogen) there will be an anion to provide charge neutrality. The anionic groups of the present invention include both units which are covalently attached to the polymer, as well as, external anions which are present to achieve charge neutrality. Non-limiting examples of anions suitable for use include halogen, inter alia, chloride; methyl sulfate; hydrogen sulfate, and sulfate. The formulator will recognize by the herein described examples that the anion will typically be a unit which is part of the quaternizing reagent, inter alia, methyl chloride, dimethyl sulfate, benzyl bromide.
X is oxygen, xe2x80x94NR4xe2x80x94, and mixtures thereof, preferably oxygen.
Y is hydrogen, C1-C4 linear alkyl, xe2x80x94N(R1 )2, or an anionic unit. Y is xe2x80x94N(R1 )2 preferably when Y is part of an R unit which is a backbone branching unit. Anionic units are defined herein as xe2x80x9cunits or moieties which are capable of having a negative chargexe2x80x9d. For example, a carboxylic acid unit, xe2x80x94CO2H, is neutral, however upon de-protonation the unit becomes an anionic unit, xe2x80x94CO2xe2x88x92, the unit is therefore, xe2x80x9ccapable of having a negative charge. Non-limiting examples of anionic Y units include xe2x80x94(CH2)fCO2M, xe2x80x94C(O)(CH2)fCO2M, xe2x80x94(CH2)fPO3M, xe2x80x94(CH2)f(OPO3M, xe2x80x94(CH2)fSO3M, xe2x80x94CH2(CHSO3M)xe2x80x94(CH2)fSO3M, xe2x80x94CH2(CHSO2M)(CH2)fSO3M, xe2x80x94C(O)CH2CH(SO3M)CO2M, xe2x80x94C(O)CH2CH(CO2M)NHCH(CO2M)CH2CO2M, xe2x80x94C(O)CH2CH(CO2M)NHCH2CO2M, xe2x80x94CH2CH(OZ)CH2O(R1O)tZ, xe2x80x94(CH2)fCH[O(R2O)tZ]xe2x80x94CHfO(R2O)tZ, and mixtures thereof, wherein Z is hydrogen or an anionic unit non-limiting examples of which include xe2x80x94(CH2)fCO2M, xe2x80x94C(O)(CH2)fCO2M, xe2x80x94(CH2)fPO3M, xe2x80x94(CH2)fOPO3M, xe2x80x94(CH2)fO3M, xe2x80x94CH2(CHSO3M)xe2x80x94(CH2)fO3M, xe2x80x94CH2(CHSO2M)(CH2)fO3M, xe2x80x94C(O)CH2CH(SO3M)CO2M, xe2x80x94C(O)CH2CH(CO2M)NHCH(CO2M)CH2CO2M, and mixtures thereof, M is a cation which provides charge neutrality.
Y units may also be oligomeric or polymeric, for example, the anionic Y unit having the formula: 
may be oligomerized or polymerized to form units having the general formula: 
wherein the index n represents a number greater than 1.
Further non-limiting examples of Y units which can be suitably oligomerized or polymerized include: 
As described herein above that a variety of factors, inter alia, the overall polymer structure, the nature of the formulation, the wash conditions, and the intended target cleaning benefit, all can influence the formulator""s optimal values for Qr, xcex94Q, and Q(+).
For granular laundry detergent compositions, preferably greater than about 40%, more preferably greater than 50%, yet more preferably more than 75%, most preferably greater than 90% of said Y units are xe2x80x94SO3M comprising units. However, those skilled in the art will recognize the number of Y units which comprise an anionic unit will vary from embodiment to embodiment depending on the particular wash conditions, surfactants, and adjunct ingredients in the formulation. M is hydrogen, a water soluble cation, and mixtures thereof; the index f is from 0 to 6.
For liquid laundry detergent compositions preferably less than about 90%, more preferably less than 75%, yet more preferably less than 50%, most preferably less than 40% of said Y units comprise an anionic moiety, inter alia, xe2x80x94SO3M comprising units. The number of Y units which comprise an anionic unit will vary from embodiment to embodiment. M is hydrogen, a water soluble cation, and mixtures thereof; the index f is from 0 to 6.
The index n represents the number of backbone units wherein the number of amino units in the backbone is equal to n+1. For the purposes of the present invention the index n is from 1 to about 99. Branching units B are included in the total number of backbone units.
The following non-limiting examples indicate the manner in which the backbones of the present polyamines are assembled and defined.
The following is an non-limiting example of a backbone according to the present invention prior to quaternization: 
which has an index n equal to 4.
The following is also a non-limiting example of a backbone according to the present invention prior to quaternization: 
which has an index n equal to 4.
The following is a non-limiting example of a polyamine backbone which is fully quaternized. 
The following is a non-limiting example of a polyamine backbone which is fully quaternized. 
The following is a non-limiting example of a final zwitterionic polyamine according to the present invention. 
The following is a non-limiting example of a final zwitterionic polyamine according to the present invention. 
Preferred zwitterionic polymers of the present invention have the formula: 
wherein R units have the formula xe2x80x94(R2O) R3xe2x80x94 wherein R2 and R3 are each independently selected from the group consisting of C2-C8 linear alkylene, C3-C8 branched alkylene, phenylene, substituted phenylene, and mixtures thereof. The R2 units of the formula above, which comprise xe2x80x94(R2O)tY units, are each ethylene; Y is hydrogen, xe2x80x94SO3M, and mixtures thereof, the index t is from 15 to 25; the index m is from 0 to 20, preferably from 0 to 10, more preferably from 0 to 4, yet more preferably from 0 to 3, most preferably from 0 to 2; the index w is from 1, preferably from about 2 to about 10, preferably to about 6.
Non-limiting examples of backbones according to the present invention include 1,9-diamino-3,7-dioxanonane; 1,10-diamino-3,8-dioxadecane; 1,12-diamino-3,10-dioxadodecane; 1,14-diamino-3,12-dioxatetradecane. However, backbones which comprise more than two nitrogens may comprise one or more repeating units having the formula:
H2Nxe2x80x94[Rxe2x80x94NH]xe2x80x94
for example a unit having the formula:
H2Nxe2x80x94[CH2CH2OCH2CH2NH]xe2x80x94
is described herein as 1,5-diamino-3-oxapentane. A backbone which comprises two 1,5-diamino-3-oxapentane units has the formula:
H2NCH2CH2OCH2CH2NHCH2CH2OCH2CH2NH2.
Further suitable repeating units include 1,8-diamino-3,6-diaxaoctane; 1,11-diamino-3,6,9-trioxaundecane; 1,5-diamino- 1,4-dimethyl-3-oxaheptane; 1,8-diamino-1,4,7-trimethyl-3,6-dioxaoctane; 1,9-diamino-5-oxanonane; 1,14-diamino-5,10-dioxatetradecane.
The present invention affords the formulator with the ability to optimize the zwitterionic polymer for a particular use or embodiment. Not wishing to be limited by theory, it is believed that the backbone quaternization (positive charge carriers) interact with the hydrophilic soils, inter alia, clay, and the anionic capping units of the R1 units ameliorate the ability of surfactant molecules to interact, and therefore occupy, the cationic sites of the zwitterionic polymers. It is surprisingly found that the amount of anionic moieties needed vary from embodiment to embodiment. Heavy Duty Granular (HDG) compositions which comprise a high amount of linear alkylbenzene sulfonate (LAS) surfactant require a greater number of anionic units per se to be present in the zwitterionic polymers. However, unexpectedly, when LAS is substituted for by a branched chain LAS surfactant, the benefit provided by the zwitterionic polymer is enhanced. Preferably, in HDG formulations, the zwitterionic polymer will have a net negative charge. For example, three quaternized backbone nitrogens will be present for every 5xe2x80x94SO3M capping units.
It is surprisingly found that the liquid laundry detergent compositions (HDL) which encompass the present invention are more effective in releasing hydrophilic soils when the backbones which comprise R units have a greater degree of alkylene unit character and which comprise an excess of backbone quaternary units with respect to the number of anionic units present.
The zwitterionic polymers of the present invention preferably comprise polyamine backbone which are derivatives of two types of backbone units:
i) normal oligomers which comprise R units of type (i), which are preferably polyamines having the formula:
H2Nxe2x80x94(CH2)x]n+1xe2x80x94[NHxe2x80x94(CH2)x]mxe2x80x94[NBxe2x80x94(CH2)x]nxe2x80x94NH2
wherein B is a continuation of the polyamine chain by branching, n is preferably 0, m is from 0 to 3, x is 2 to 8, preferably from 3 to 6; and
ii) hydrophilic oligomers which comprise R units of type (ii), which are preferably polyamines having the formula:
H2Nxe2x80x94[(CH2)xO]y(CH2)x]xe2x80x94[NHxe2x80x94[(CH2)xO]y(CH2)x]mxe2x80x94NH2
wherein m is from 0 to 3; each x is independently from 2 to 8, preferably from 2 to 6; y is preferably from 1 to 8.
Depending upon the degree of hydrophilic character needed in the zwitterionic backbones, the formulator may assemble higher oligomers from these constituent parts by using R units of types (iii), (iv), and (v). Non-limiting examples include the epihalohydrin condensate having the formula: 
or the hybrid oligomer having the formula: 
wherein each backbone comprises a mixture of R units.
As described herein before, the formulator may form zwitterionic polymers which have an excess of charge (Qr less than 1 or greater than 1) or an equivalent amount of charge type (Qr equal to 1). An example of a preferred zwitterionic polyamine according to the present invention which has an excess of anionic charged units, Qr equal to 2, has the formula: 
wherein R is a 1,3-propyleneoxy-1,4-butyleneoxy-1,3-propylene unit, w is 2; R1 is xe2x80x94(R2OtY, wherein R2 is ethylene, each Y is xe2x80x94SO3xe2x88x92, Q is methyl, m is 0, n is 0, t is 20. For zwitterionic polyamines of the present invention, it will be recognized by the formulator that not every R1 unit will have a xe2x80x94SO3xe2x88x92 moiety capping said R1 unit. For the above example, the final zwitterionic polyamine mixture comprises at least about 90% Y units which are xe2x80x94SO3xe2x88x92 units.
As described herein before, the formulator may form zwitterionic polymers which have an excess of charge or an equivalent amount of charge type. An example of a preferred zwitterionic polyamine according to the present invention which has an excess of backbone quaternized units, has the formula: 
wherein R is a 1,5-hexamethylene, w is 2; R1 is xe2x80x94(R2O)tY, wherein R2 is ethylene, Y is hydrogen or xe2x80x94SO3M, Q is methyl, m is 1, t is 20. For zwitterionic polyamines of the present invention, it will be recognized by the formulator that not every R1 unit will have a xe2x80x94SO3 moiety capping said R1 unit. For the above example, the final zwitterionic polyamine mixture comprises at least about 40% Y units which are xe2x80x94SO3xe2x88x92 units.